Process for optically brightening, dyeing or printing fibrous materials



United States Patent The present invention is based on the observation that fibrous materials, especially textile materials, for example, fibres, filaments, flocks, woven fabrics and knitted fabrics, can be dyed, optically brightened or printed fast to washing when the material is treated in the presence of alkaline reacting substances, if necessary, at an elevated temperature, with fluorescent brighteners or dyestuffs that contain one or more reactive hydrogen atoms preferably bound through nitrogen, oxygen or sulphur atoms or that are capable of forming one or more such hydrogen atoms during the dyeing or printing process and that do not contain fibre-reactive groupings, and with quaternary hydrazine compounds not having dyestuff character and thatcorrespond to the formula to B and another is bound to R B,represents an acidify-' ing substituen't, R represents a low-molecular alkenyl or halogenated alkyl group bound through an SO or a -CO bridge, R represents a non-aromatic hydrazine residue containing a'lquaternary nitrogenatom bound directly to Y and in which residue the quaternary nitrogen atom is bound to its 'substituents by single bonds, the ring containing the quaternary nitrogen atom being of saturated character incyclic compounds, n is 1, 2 or 3, m is the valency of the anion and the anion is the negative residue of a monobasic or polybasic acid.

The new process is eminently; suitable for dyeing or printing textile materials made from natural and/or regenerated cellulose, but it is also suitable for textile materials made from polyacrylonitrile' or copolymers of acrylonitrile and other vinyl compounds, or for textile materials made from linear polyesters, for example, polyethylene glycol terephthalate or polyesters based on terephthalic acid and, para-dimethylol-cyclohexane, as well as for natural and synthetic polyamide fibres, for example, silk, wool, polyhexamethylene adipic acid amide (nylon), polyaminoundecanoic' car'boxylic acid amide (Rilsan), paper and leather. 1

The alkaline reacting substances used are preferably inorganic substances, especially alkali metal hydroxides or carbonates, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, trisodium phosphate or potassium carbonate. However, it is also possible to use compounds that are converted into sub stances having a stronger alkaline action under the normal conditions obtaining during 'dyeing or printing, for

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example, alkali metal bicarbonates, for example, sodium or potassium bicarbonate, as well as dialkali metal phosphates, for example, disodium phosphate. It is also possible to use mixtures of two or more alkaline substances. Use may also be made of organic bases, for example, trimethylbenzylammonium hydroxide, or compounds that yield dissociation products having a basic reaction only when heated, for example, sodium trichloroacetate.

Suitable dyestuffs are azo dyestuffs, for example, mono-, disor poly-azo dyestuffs, metal-complex dyestuffs, anthraquinone, azomethine, triphenylmethane, oxazine or dioxazine dyestuffs or tetrazaporphin, for example, phthalocyanine dyestuflfs, and suitable fluorescent brighteners are fluorescent compounds of the stilbene, benzimidazole, benzoxazole or benzthiazole series. In the process of the invention it is also possible to use mixtures of two ormore dyestuffs.

The dyestuffs of the kind defined and the fluorescent brightening agents 'to be used in the process of the invention contain one or more reactive hydrogen atoms preferably bound through nitrogen, oxygen and/or sulphur atoms, for example, in the form of primary or secondary amino groups, sulphonic acid amide groups, sulphonic acid alkylamide groups, for example, of the kind having low-molecular alkyl residues, sulphonic acid arylamide groups, for example, sulphonic acid anilide groups, carboxylic acid amide groups, carboxylic acid alkylamide groups, for example, of the kind having low-molecular alkyl residues, hydroxyl groups and/or sulphhydryl groups, but they are free from fibre-reactive groups (for example, sulphatoethylsulphone, sulphato or halogenethyl sulphamide, 'fi-sulphato or fl-halogenpropionyl, acrylic, halogenpyrimidyl or halogenated triazine groups, halogenated quinazoline or quinoxaline groups, 2-halogenated benzthiazole or halogenated pyridazone groups and the like). Of special technical interest are those dyestuff that contain one or more reactive hydrogen atoms in the form t of sulphonic acid amide groups, for example, dyestuffs stuffs of the kind defined free from sulphonic acid groups thatcontain one atom of chromium or cobalt bound in complex union with two monoazo dyestulf molecules.

, The term fluorescent brighteners or dyestuffs containbig .one or more reactive hydrogen atoms is intended to indicate that the brighteners and dyestuffs of the kind defined contain one or more active hydrogen atoms that enable them to enter into the so-called Michael addition reaction.

The new process is suitable for the application of both dyestuffs and brighteners that are free from groups imparting solubility in water as well as water-soluble dyestuffs. The water-soluble dyestufls generally contain one or more sulphonic acid and/ or carboxyl groups as groups imparting solubility in water. In the process of the invention it is advantageous to use dyestufls containing one or more sulphonic acid amide or sulphonic acid alkylamide groups, for example, sulphonic acid-(fl-hydroxyethyD- amide or sulphonic acid methylamide groups as groups imparting solubility in water. The dyestuffs used may be substantive dyestuffs, but they must not be so-called reactive dyestutfs, that is to say, dyestuffs capable of being fixed to the substratum to be dyed or printed by a chem ical bond. In the case of substantive dyestuffs, the new 3. process improves the properties of fastness of the dyeings and prints.

The quaternary hydrazine compounds of the Formula.

1 do not have dyestufi characteristics and must thus be incapable of colouring the substratum, nor must they possess distinct colour of their own. They comprise the residue of the formula The symbol B in the Formula 1 represents an acidifying substituent whose constitution may differ widely. For example, B may represent a carboxylic acid amide group bound to Y through its carbon atom. However, B is ad vantageously a .CO--- or an SO bridge.

The residue R may be unsaturated or saturated. The principal unsaturated residues that may be mentioned are the vinylsulphone residue, acrylic residues (for example chloracrylic, bromacrylic, and the unsubstituted acrylic residue itself) and crotonyl residues, for example, the chlorocrotonyl residue. Saturated low-molecular alkyl residues represented by R that may be mentioned are, for example, the residue of the formula CEHCH-OH2-OCHPCHFCO o and the 3-chloropropionyl as well as the fi-bromopropionyl residue.

The hydrazine reside R in the Formula 1 contains a quaternary nitrogen atom which is directly bound to the bridging group Y and which also satisfies the conditions i those in which one or both of the hydrazine nitrogen.

atoms may be members of one or more than one ring.

In addition to one or a plurality of hydrazine groups,

theresidue R may contain substituents that do not react with the fluorescent brighteners or dyestulfs to be used, for example, halogen atoms, nitro, alkoxy or hydroxyl groups. Preferably, however, hydrazines are used that contain only carbon and hydrogen atoms in addition to at least one group of'the formula for example, hydrazines containing at least one tertiary nitrogen atom that are substituted exclusively by nonaromatic hydrocarbon residues.

Hydrazines of the kind defined may correspond, for example, to the formula in which R and R represent aliphatic hydrocarbon residues containing not more than 4 carbon atoms and 4 R represents a residue of the same kind, an HS-CS- group, an H0 5- group, a group of the formula or preferably a hydrogen atom, or in which R and R together with nitrogen atom form a ring, preferably a 5- membered or 6-membered ring.

The purely aliphatic hydrazines of the Formula 5 advantageously correspond to the formula m pl 2nl) in which m and it each represent an integer not greater than 4, but preferably 1, and p represents an integer not greater than 5. The aliphatic hydrocarbon residues in these hydrazine compounds may be branched but they are preferably unbranched.

Finally, emphasis must be given to those hydrazine compounds in which the nitrogen atoms that are adjacent to each other are at the same time members of two condensed rings, for example, of the formula 1,5-diaza-bicyclo-(0,3,3)-octane of the formula (10) /0 H2 Oil CH2 CHI CH2 CH:

( Alkyl H N N Alkyl S 03H HsC\ /H HaC 50 E Alkyl fi NNHr-C --SH .Alkyl NNH-C SH Ha C (15) C Hz-C Hg CHs-N NNH;

0 Hz- 0 g Specific illustrative compounds employable according to the present mventlon are treating the material to be optically brightened, dyed or CHz-OH: 963$ CO-GH CHg-N CH I l NH: CHz-Cfiz CHg-CH; 0%, CH1 CHz-CH: CH1 N-CHCH-CCh-Ih N-COOHCHN /CH1 GHQ-CH: NH H, N 2 CHa-CHz sol printed successively with the alkaline substances, the v dyestutfs and the colourless hydrazine compounds of the kind defined above in any desired sequence. However, it CH 0h: CH: is advantageous to treat the material in a dyebath or with a printing paste that contains the alkaline substance, the

| 16 dyestufl or dyestufis and the colourless hydrazine com- C pounds of the kind defined above. The material so treated 99 CO-(JHz-CHg-CI is then rinsed in the usual manner, soaped if necessary, I and finished in the usual manner. It is also of interest to use dyestufi preparations that contain, in addition to the F dyestuffs, the colourless hydrazine compounds of the kind HNNOH-.OHCON N-CO-CHl-CHQ-N-NHB defined above together with dispersing agents and/or dye- 2 C19 H, (IJH' ing or printing assistants.

v I The hydrazine compounds may also be used in a state of fine division together with dispersing or wetting agents t ahloh e he the hegahve P 4 of a h or as solutions in solvents miscible with water. baslc Polyhaslc, Preferably lhorgahlc The resldue 40 In addition to the alkaline reacting substances, dyestuffs of the kind defined that are the most important are prr' and, colourless hydrazine compounds, the dyebaths and manly halogen Preferably 4041-16- Q printing pastes used in the process of the invention may 4 z because they are eashy ohtzhhahleflhut thls contain the usual dyeing and printing assistants, provided naturally does not other aPPIOPrlate Tesldues' the said assistants do not react in an undesirable manner The quaternary hydrazlhe compounds of the Formula with the starting materials. Dyeing and printing assistants 1 can be 1 spared by Teachhg compounds of the formula of the kind defined are, for example, surface-active compounds for example, alkylsulphonates or compounds that l prevent migration of the dyestuff, for example, sodium H1O CH acetate, or substances that improve the solubility and fixal l l tion of the dyestuffs, for example, urea, or thickening agents, for example, oil-in-water emulsions, tragacanth g thickeners, alignates or methyl cellulose. in which R and n have the meanings given abovefwith a rule t dyebaths and prmtmg pastes are applied tertiary hydrazines in a molecular ratio of 1:1, 152 or to e mammal treated by f of a paddmg mangle or by printing. However, it is also possible to 1:3. Instead of starting from the halogenated compounds, car i ry out the process of the invention in other kinds of the reaction may also be carried out with the correspondconventiohal dyeing apparatus for example on a ji v se mg esters of Polybaslcmorgam; 1 1 h t -1Il an open beck, on a W111Ch or in a clrculatlng liquor Quatenlary compouilds of e ormu a t at con am machine. When treating textile materials made from celan NN'dlalkylhydhazme resldue hound Y i also lulosic fibres by the new process it is also possible to obtainable by reacting the appropriate tertiary nitrogen bases with chloramine.

In accordance With the process of the invention it is advantageous to use polyfunctional compounds of the Formula 1, that is to say, compounds in which n is at least 1, especially those in which n is 3.

When working according to the new process, fixation of the fluorescent brighteners or dyestuffs on the substratum can be brought about at room temperature, that is to say, at about 15 to 30 C. It is advantageous, how-" ever, to fix the dyestuffs in the usual manner, for example, by steaming or by a dry heat treatment at, a temperature between 30 and 200 C., preferably between 40 and 150 0., provided the material to be dyed and/or printed permits the use of these temperatures. The duration of the fixing process can vary within wide limits because 6 it depends on the nature of the dyestuff, hydrazine compound, alkaline substance and substratum used and on the temperature at which fixation is carried out; however, it is easily determined by tests. Fixation of dyestulfs or fluorescent 'brighteners on textile material made of cellulose is advantageously carried out by steaming or a dry heat treatment at to 150 C. and is generally completed within approximately 5 to 10 minutes in this temperature range.

The process of the invention can be carried out by impart a finish to the material, for example, a creaseresist finish, at the same time as it is being dyed or printed.

In the new process for dyeing, printing or optically brightening textile materials it is advantageous to use 100 parts each of the fluorescent brightener or dyestuff containing one or more reactive hydrogen atoms preferably bound through nitrogen, oxygen or sulphur atoms,

' approximately 10 to 200 parts of a strong alkaline sub- 0 stance and approximately 20 to 400 parts of colourless hydrazine compound of the kind defined.

The optical brightening effects, dyeings and prints obtainable by the process of the invention are generally distinguished by excellent properties of Wet fastness. When using water-soluble dyestufls it is advantageous to A printing paste having the following composition is prepared: 30 parts of the 1:2 chromium complex com-- pound of the monoazo dyestutf of the formula 100 parts of urea, 30 parts of the compound of the formula CH: C OCHgCHg-II-NH1 I l (H13 Oz CHg CH;

I\|ICOCHTCHTI.INH2

30 parts of 30% sodium hydroxide solution, 400 parts of sodium alginate thickener 60:1000, 410 parts of water.

A cotton fabric is roller-printed with this paste. The

materialis then dried, steamed for 8 minutes and then vigorously rinsed, first hot and then cold.

A bluish green print:which is fast to washing at the boil is obtained.

Similar good results are obtained when the above dyest-ufi is replaced by any one of the dyestuffs listed in C01 umn I of the following table; Column H indicates the tints obtained.

I II

1:1 chromium complex. compound 01 the monoazo-dyestufl. of the formula SOzNH:

Orange.

S O zNHz 1:2 cobalt complex compound 01 the mouoazo dyestufi of the formula OzNH:

Red.

lEIIO 1:2 cobalt complex compound of the monoazo dyestufi o! the tormula Claret.

1:2 chromium-complex compound of the monoazo dyestufi of the formula Oil HsN Blue.

1:2 chromium complex compound of the monoazo dyestufl of the formula Yellow.

CH Cl I II 6 1:2 chromium complex compound of the monoazo dyestufi 01' the Violet.

formula OH HO HzN-OzS N=N 7 1:2 chromium complex compound of the formula Brown.

%N- (140mm 0 N H2N-O2S ll N=N-C CH 8 [copper phthalocyanine](SOzNHCHzCHzOH) Blue.

CHz-C HQOH 9 [copper phthalocyanlne1- SO2N Blue.

CH2-C HaoH 4 10 (1? NH; Blue.

SO H NH: 1 i 0 NH NH N =K 11- [tetraphcnyl copper phthalocyam'ne Green.

(SO2-NHCH2CH2OH)g 12- [copper phthalooyanine Blue.

13- 1:2 chromium complex compound of the dye of the formula Reddish oran e. OH HO g N S 0 3H HzN-SOz CH;

14 1:2 cobalt-complex compound of the formula 13 Yellowbrown.

15 1:2 chromium complex compound of the formula Red.

H O :S 0 H H O I l N M u N S O z-NH2 C1 CH3 NH SOPNHOSOKH 2 16...--- [copper phtha1ocyan1ne{ Tlfiquoise ue; S 0 3H I i II I II soda SQT-NHGNHD 3 17 [nickel phthalocyaninei Turquoise blue. SOaH Exam le 2 The padded material is dried, subjected to a heat treatp 15 6 Q d d th d t A cotton fabric isspadded with a liquor of the-fol'low- 3 2 55? 5 mmutes at 1 nnse an en scape a 3 :2 1 ?gggg g g rggg i gfi gfigf 3; 3 252;: T1126 fluorelalscgntlbrightening effect so obtained is fast to was ing att e 01. dyestufi of the formula What is 61 aime d is:

OH OH 1. A process, wherein fibrous material is treated in the presence of an alkaline reacting substance with a compound A selected from the group consisting of a fluorescent brightener and a dyestufl? that, is free from fiber-re- OIS active substitutents and that contains a member selected C: from the group consisting of a reactive hydrogen atom and H! a group capable of forming a reactive hydrogen atom 200 parts of urea, 40 parts of the compound of the during the process and a compound B which is a colorless form la polyfunctional hydrazine compound of the formula CH l 0 0H 0H 1 I IH 69% F Hi0 CH: CH3 H on cu on T o B-Y-R1 ).,(An10n )n,m E1N-NC-CHzOHaCO--N N-oo-omom-N-Nrn H, n L C e in which Y represents a member selected from the group H1 301 consisting of a methylene, ethylene and propylene bridg- 20 parts of sodium carbonate, 710 parts of water. ing group, B represents a member selected from the group The padded fabric is dried and then subjected to a heat 40 consls ing of an --SO and a -CO bridge, R repretreatment for 5 minutes at 160 C. It isthen thoroughly sents a member selected from the group consisting of rinsed, fir t hot and then cold, chloracetyl, acryl, chloracryl, ibromacryl, crotonyl, chloro- A red dyeing fast to washing at the boil is obtained. crotonyl, fil p lf B- p p y fl-( P Y- Similar good results are obtained when the above-men- -P P Y)P P y Y f=, 3-chlorethylsulfone tioned hydrazinium compound is replaced by an equal proand 3-slllfatoethylsulfone, IS a Posltlve Whole number P portion of the compound of the formul to 3, m is the valency of the anion and the anion is the negative radical of a monobasic or polybasic acid and H N CH CH 2 gee R represents a non-aromatic hydrazine radical of the CI7O CH=CHN group' consisting of N\ CHa-CH: CH r-OH; n, on, CHz-CH: T'Q I -ornourooaq N-oo-oH,oH:-N T H,- H, NH; 0 NH; ens-0H, e H 7 H: 301 I in wh1ch R, and R represent aliphatic hydrocarbon radi- Example 5 cals containing not more than 4 carbon atoms andR A cotton fabric is padded with a liquor having the folrepre sents a member selectedfiom thefigrpup consisting of lowing composition: 3 parts of the'fluorescent bright an allphatlc hydrocarbon radical containing'not more than t ing agent of the formula 4 carbon atoms, an HS-CS-group, an HO S-group, a

group of the formula 110 e N r on Or g N-alkylene -C C-CH3-SO3NH: R1

0 and a hydrogen atom and in wh1ch-R and R and R and 5 R respectively together with the nitrogen atom can form 50 Parts of urea, 5 P 0f the compound of the formula a 5-' or 6-membered ring and r and s are numbers not on, @939 smaller than 3 and not greater than 4. l 2. Aprooess as claimed in claim 1 wherein the fibrous 1 material used is a textile material. /N\ CH; 3. A process as claimed in claim 1 wherein the fibrous H, H, material is treated at an elevated temperature. a l l l 4. A processes claimed in claim 1 wherein the com- I p e t pound A contains in the molecule at least one reactive 0H. 0H, CH; 301

5 parts of sodium carbonate, 937 parts of water.

hydrogen atom bound through a nitrogen, oxygen, or

sulfur-atom, to t s 5. A process as claimed in claim 1, wherein a dyestnfi containing a sulphamide group is used.

6. A process as claimed in claim 1, wherein a dyestufi free from sulfonic acid group is used.

7. A process as claimed in claim 1, wherein a 1:2- chromium-complex compound of a monoazo dyestuff is used.

8. A process as claimed in claim 1, wherein a 1:2- cobalt-complex compound of a monoazo dyestuff is used.

9. A process as claimed in claim 1, wherein the radical B in the given formula is a CO bridge.

10. A process as claimed in claim 1, wherein the radical Y in the given formula is ethylene.

11. A process as claimed in claim 10, wherein R corresponds to the formula rl lrl) in which m and n each represent an integer not greater than 4 and p represents an integer not greater than 5.

12. A process as claimed in claim 1, wherein n stands for 3.

13. A process as claimed in claim 1, wherein the radical R is the radical of a cyclic hydrazine.

14. A process as claimed in claim 1, wherein the radical R is the radical of N,N-dimethy1hydrazine.

15. A process as claimed in claim 1, wherein the compound A is fixed on the fibrous material by steaming.

16. A process as claimed in claim 1, wherein the compound A is fixed on the fibrous material by a dry heat treatment.

17. A process as claimed in claim 1, wherein the fibrous material is treated successively with the alkaline reacting substance, the compound A and the colorless hydrazine compound in any desired sequence.

18. A process as claimed in claim 1, wherein the fibrous material is treated in the presence of a dispersing agent.

19. A process as claimed in claim 1, wherein parts each of compound A, 10 to 200 parts of a strong alkaline substance and 20 to 400 parts of the hydrazine compound are used.

20. A process as claimed in claim 1, wherein cellulosic:

fibrous material is treated.

References Cited UNITED STATES PATENTS 3,190,871 6/1965 Basel 81 FOREIGN PATENTS 609,825 4/1962 Belgium. 1,358,724 3/1964 France.

4/1964 France.

OTHER REFERENCES Ciba, Swiss Auslegeschrift 12534/ 62, pub. 7/15/64. Only pp. 1-15 are relied upon.

DONALD LEVY, Primary Examiner.

UNITED STATES PATENT ormom CERTIFICATE OF CORRECTION Patent No. 3,347,617 October 17, 1967 Paul Ulrich et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 12, lines 30 to 35, the formula should appear as shown below:

N H 0 CH2 I! b EB Y R6) (A' 111011 l n n/m (3 Hz J Signed and sealed this 21st day of October 1969.

(SEAL) Attest:

w EDWARD M.FLETCHER,JR.

Attesting Officer Commissioner of Patents WILLIAM E. SCHUYLER, JR. 

1. A PROCESS, WHEREIN FIBROUS MATERIAL IS TREATED IN THE PRESENCE OF AN ALKALINE REACTING SUBSTANCE WITH A COMPOUND A SELECTED FROM THE GROUP CONSISTING OF A FLUORESCENT BRIGHTER AND A DYESTUFF THAT IS FREE FROM FIBER-REACTIVE SUBSTITUTENTS AND THAT CONTAINS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A REACTIVE HYDROGEN ATOM AND A GROUP CAPABLE OF FORMING A REACTIVE HYDROGEN ATOM DURING THE PROCESS AND A COMPOUND B WHICH IS A COLORLESS POLYFUNCTIONAL HYDRAZINE COMPOUND OF THE FORMULA 